4,5-Bis[di(2-pyridylmethyl)aminomethyl]imidazole | 256464-12-7

• 分子结构分类: 有机化合物 - 有机杂环化合物 - 吡啶及其衍生物
• 英文名称: 4,5-Bis[di(2-pyridylmethyl)aminomethyl]imidazole
• 英文别名: 4,5-bis(di(2-pyridylmethyl)aminomethyl)imidazole；N-[[4-[[bis(pyridin-2-ylmethyl)amino]methyl]-1H-imidazol-5-yl]methyl]-1-pyridin-2-yl-N-(pyridin-2-ylmethyl)methanamine
• CAS: 256464-12-7
• 化学式: C₂₉H₃₀N₈
• 分子量: 490.611
• InChiKey: ORAJWXXVFNETII-UHFFFAOYSA-N

计算性质

• 辛醇/水分配系数(LogP)：
  1.6
• 重原子数：
  37
• 可旋转键数：
  12
• 环数：
  5.0
• sp3杂化的碳原子比例：
  0.21
• 拓扑面积：
  86.7
• 氢给体数：
  1
• 氢受体数：
  7

反应信息

• 作为反应物：
  描述：

  copper(II) perchlorate hexahydrate 、 4,5-Bis[di(2-pyridylmethyl)aminomethyl]imidazole 在 NEt₃ 作用下， 以 甲醇 为溶剂， 生成
  参考文献：
  名称：

  A novel imidazolate-bridged copper–zinc heterodinuclear complex as a Cu, Zn–SOD active site model

  摘要：

  合成了一种含有两个金属结合基团的咪唑衍生物咪唑桥联Cu(II)-Zn(II)异双核配合物，并阐明了其结构和性能。

  DOI：

  10.1039/a906226b
• 作为产物：
  描述：

  二甲基吡啶胺 、 imidazole-4,5-dicarbodialdehyde 在 sodium cyanoborohydride 、 溶剂黄146 作用下， 以 甲醇 为溶剂， 反应 72.0h， 以80%的产率得到4,5-Bis[di(2-pyridylmethyl)aminomethyl]imidazole
  参考文献：
  名称：

  A novel imidazolate-bridged copper–zinc heterodinuclear complex as a Cu, Zn–SOD active site model

  摘要：

  合成了一种含有两个金属结合基团的咪唑衍生物咪唑桥联Cu(II)-Zn(II)异双核配合物，并阐明了其结构和性能。

  DOI：

  10.1039/a906226b

文献信息

• Synthesis and Characterization of Imidazolate-Bridged Dinuclear Complexes as Active Site Models of Cu,Zn-SOD
  作者：Hideki Ohtsu、Yuichi Shimazaki、Akira Odani、Osamu Yamauchi、Wasuke Mori、Shinobu Itoh、Shunichi Fukuzumi

  DOI：10.1021/ja994050j

  日期：2000.6.1

  New dinucleating ligands having two metal-binding sites bridged by an imidazolate moiety, Hbdpi and HMe(4)bdpi (Hbdpi = 4,5-bis(di(2-pyridylmethyl)aminomethyl)imidazole, HMe(4)bdpi = 4,5-bis(di(6-methyl -2-pyridylmethyl)aminomethyl)imidazole), have been designed and synthesized as model ligands for copper-zinc superoxide dismutase (Cu,Zn-SOD). The corresponding mononucleating ligand, MeIm(Py)(2) (MeIm(Py)(2) = ((1-methyl-4-imidazolyl)methyl)bis(2-pyridylmethyl)amine), has also been synthesized for comparison. The imidazolate-bridged Cu(II)-Cu(II) homodinuclear complexes represented as [Cu-2(bdpi)(CH3CN)(2)](ClO4)(3). CH3-CN . 3H(2)O (1), [Cu-2(Me(4)bdi)(H2O)(2)](ClO4)(3). 4H(2)O (2), a Cu(II)-Zn(II) heterodinuclear complex of the type of [CuZn(bdpi)(CH3CN)(2)](ClO4)(3). 2CH(3)CN (3), and a Cu(II) mononuclear complex of [Cu(MeIm(Py)(2)(CH3CN)](ClO4)(2). CH3CN (4) have been synthesized, and the structures of complexes 1-4 were determined by X-ray crystallography. The Cu(II)-Zn(II) distance of 6.197(2) Angstrom in 3 agrees well with that of native Cu,Zn-SOD (6.2 Angstrom). All the metals in 1-4 have pentacoordinate geometries with the imidazolate or 1-methylimidazole nitrogen, two pyridine nitrogens, the tertiary amine nitrogen, and a solvent (CH3CN or H2O). The coordination site occupied by a solvent can be susceptible to ligand substitution, providing a binding site for substrate superoxide. Magnetic measurements of the Cu(II)-Cu(II) homodinuclear complexes 1 and 2 have shown an antiferromagnetic exchange interaction with a coupling constant of -2J = 73.4 and 145.9 cm(-1), respectively. The ESR spectra of 1 and 2 exhibited broad signals centered at g congruent to 2.13 due to the spin-spin interaction between two copper ions, while the ESR spectrum of the Cu(II)-Zn(II) heterodinuclear complex 3 showed a signal which is characteristic of mononuclear trigonal-bipyramidal Cu(II) complexes (g(parallel to) = 2.10, g(perpendicular to) = 2.24, /A(parallel to)/= 11.7 mT, and /A(perpendicular to)/= 12.4 mT). The cyclic voltammograms of homodinuclear complexes (1 and 2) in CH3CN gave two reversible waves which correspond to the Cu(I,I)/Cu(I,II) and Cu(I,II)/Cu(II,II) redox processes: E-1/2 = -0.31 and -0.03 V vs Ag/AgCl for 1 and E-1/2 = -0.29 and +0.12 V vs Ag/AgCl for 2, respectively. On the other hand, the Cu(II)-Zn(II) heterodinuclear complex 3 exhibited one Cu(I)/(II) reversible wave, E-1/2 = -0.03 V vs Ag/AgCl, which is shifted in a positive direction (0.21 and 0.19 V) as compared to those of the corresponding Cu(II) mononuclear complexes. All the examined complexes catalyzed the dismutation of superoxide at biological pH; the SOD activity increased in the order 2 < 1 < 3.